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Terry Engelhardt
Application Development Manager –
Drinking Water
Hach Company
1
HOCl vs. OCl-
2
Hypochlorite Salts
• Salts used for chlorination include
– Lithium hypochlorite LiOCl
LiOCl + H20 Li+ + HOCl + OH-
– Sodium hypochlorite NaOCl
NaOCl + H20 Na+ + HOCl + OH-
– Calcium hypochlorite Ca(OCl)2
Ca(OCl)2 + 2H20 Ca2+ + 2HOCl + 2OH-
3
Breakpoint Curve
Free Residual
Breakpoint
Dichloramine
predominates
Monochloramine
predominates
A B C
Chlorine Added
4
Chloramination
Chloramine Formation
• Monochloramine - NH2Cl
NH3 + HOCl NH2Cl + H2O
• Dichloramine - NHCl2
NH2Cl + HOCl NHCl2 + H2O
• Tricholoramine (Nitrogen Trichloride) - NCl3
NHCl2 + HOCl NCl3 + H2O
• Chloramines are not as effective disinfectants as
free chlorine
10
5
Definition of Unreacted Ammonia
• Ammonia in solution as
– NH3 Free ammonia gas dissolved in water or;
– NH4- The ammonium ion
11
Free Ammonia
Total Residual Chlorine
Total and Free Ammonia
Chlorine Added
12
6
Calculate Ratio as Cl2:N!
Atoms/
Ammonia, Atomic
molecule
NH3 mass
Nitrogen 14 X 1 = 14
Hydrogen 1 X 3 = 3
Molecular
= 17
Weight (Mass)
3 x 100
Percent Hydrogen = 17.6
17
If the feed rate is calculated on NH3 as NH3 instead of as N,
the feed rate is off 17.6%!
13
90 10
• Distribution of
80 20
chloramine
species is
% Monochloramine
70 30
% Dichloramine
60 40 effected by:
50 50
40 60
– pH
– Ammonia
30 70
20 80
10 90
concentration
(see breakpoint curve)
0 100
5 6 7 8 9
pH
14
7
Comparison of Methods
Method Range Detection %RSD Use Skill
mg/l Level*
DPD colorimetric 0-5 0.005 1-2 F&T 1
Ultra low-range
0-0.500 0.002 5-6 T 2
DPD colorimetric
DPD titration 0-3 0.018 2-7 F&T 2
Iodometric Up to Total
1 NR 2
4% Oxidants
Amperometric
Up to 10 0.015 1-2 F&T 3
Titration - Forward
-Back 0.006-1 0.006 15 T 3
Electrode Total
0-1 0.05 10 2
Oxidants
Monochlor-F W 0-4.5 Mono-
0.09 2 1
WW 0-10 chloramine
Skill Level: 1= Minimal training; 3 = Experienced
*Under ideal laboratory conditions. Practical limit for all
methods is really about 0.02
15
H H H H H H H H
N+ N+ N+
Cl2
+
N+ N+ N+
Et Et Et Et Et Et
H
AMINE WÜRSTER DYE IMINE
(colorless) (magenta colored) (colorless)
16
8
DPD Würster Dye Absorbance Curve
530 nm
Maximum sensitivity 512 nm 553 nm
510-515 nm
0.2500
Absorbance
0.1500
0.0500
Chlorine – DPD
Chloramination – MonoChlor F
18
9
Measuring Free and Total Residual
19
Test Kits
Compara Test
-tors Strips
Chlorine X X
MonoChloramine NA NA
20
10
Common Interferences
• Other oxidants: ClO2, • Buffer capacity
O3, Br2, H2O2, I2, • Sample color
KMnO4 • Mn+3 to Mn+7
• Disinfection by- • Cr +7
products, I.e. chlorite
• Organic N-Cl (organic
and chlorate
chloramines in
• Particulate wastewater)
contamination -
turbidity
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11
Chemistry of Amperometric Titration
• For total chlorine determinations, KI is oxidized by chlorine and
chloramines, at pH 4, to form tri-iodide:
I 3− + 2e − → 3I −
• Stoichiometry is thus 2:2 (titrant : sample)
PhAsO + 4 H 2 O → PhAsO(OH )2 + 2 H 3O + + 2e −
Forward Titration
• Amperometry
– Electrochemical technique in which a small electrical
voltage is applied across two electrodes
– Chemical reactions caused by titrant addition cause a
change in current, which is measured and recorded
by the instrument
12
Forward Titration
• Amperometry
– Results are obtained by calculating the current
change as a function of the amount of titrant added
Forward Titration
• Amperometry
– A potential is applied across the electrodes prior to
the titration.
– Buffer is added to the sample and KI is added to total
chlorine samples
Potential Applied
13
Forward Titration
• Amperometry
– Current can flow as long as there is a substance that
can be reduced at the cathode (+) and oxidized at the
anode (-).
+ -
Forward Titration
• Amperometry (for free residual chlorine)
– Chlorine is titrated with PAO titrant. The chlorine is
reduced at the cathode. The PAO is oxidized at the
anode.
14
Forward Titration
• Amperometry
– The more chlorine (or oxidant) in solution, the greater
the amount of current flow.
Current
Forward Titration
• Amperometry
– As the PAO titrant is added, the PAO reduces the
chlorine, and the chlorine concentration decreases.
15
Forward Titration
• Amperometry
– As the chlorine concentration decreases, the amount
of current also decreases.
Current
Forward Titration
• Amperometry
– When all of the chlorine has been reduced by the
PAO, the amount of current falls to near zero.
Current
16
Forward Titration
• Amperometry
– The chlorine concentration is calculated based on the
amount of PAO added to reduce the measured
current to zero.
Titrant
delivery
system
Dual Platinum
or
Silver/Platinum
Electrode Microampere
1.123
meter
Magnetic
Stirrer
34
17
Forward Titration
Amperometric
Probe – Free or
Total Chlorine
Monochlor F –
Monochloramine,
Colorimetric
Free and Total
DPD – Free or
Ammonia
Total Chlorine
36
18
Online Chlorine Monitoring –
Major Technologies
Colorimetric: Amperometric:
measuring intensity of color developed measuring electrical current
by reaction of chlorine with indicator generated in a circuitry by reaction of
(chemical compound, e.g. DPD). The chlorine with electrodes . The larger
deeper color, the higher chlorine current value, the higher chlorine
concentration. concentration.
Main Differentiators: Main Differentiators:
• Independent of major sample • No chemical reagents required
parameters (pH, flow, temperature),
• Fast response to analyte
• Established calibration curve concentration changes
Really?
37
Colorimetric Amperometric
Pros Pros
•Accuracy - no calibration •Fast response
•Unattended operation •Reagentless technology
(up to 30 days)
•No waste stream?
•Predictable and simple
maintenance
•Results independent of
changes in sample pH, Really?
temperature, conductivity,
sample pressure
38
19
Online Chlorine Monitoring Comparison
Colorimetric Amperometric
Cons Cons
•Reagents and waste •Greater influence from
stream management sample pH, temperature,
flow, pressure, Cl2
concentration, etc.
39
40
20
CL17 Chlorine Analyzer Pocket Colorimeter
42
21
Contact Information
N Illinois S Illinois
Paul Gauger Brad Baldwin
Hach Company Hach Company
800-227-4224 X2060 800-227-4224 X2327
pgauger@hach.com bbaldwin@hach.com
Terry Engelhardt
Hach Company
Application Development Manager –
Drinking Water
800-227-4224 X2327
tengelha@hach.com
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